CN1412236A - Fluorine-containing copolymer, polymer electrolyte containing the same and lithium cell using said electrolyte - Google Patents

Fluorine-containing copolymer, polymer electrolyte containing the same and lithium cell using said electrolyte Download PDF

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CN1412236A
CN1412236A CN02127041A CN02127041A CN1412236A CN 1412236 A CN1412236 A CN 1412236A CN 02127041 A CN02127041 A CN 02127041A CN 02127041 A CN02127041 A CN 02127041A CN 1412236 A CN1412236 A CN 1412236A
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黄胜湜
赵命东
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Samsung SDI Co Ltd
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Abstract

Provided are a fluoride copolymer, a polymer electrolyte comprising the fluoride copolymer, and a lithium battery employing the polymer electrolyte. The polymer electrolyte preferably includes as the fluoride copolymer at least one fluoride polymer selected from a polyethylene glycol methylether (meth)acrylate (PEGM)A)-2,2,2-trifluoroethylacrylate (TFEA) polymer, a PEGMA-TFEA-acrylonitrile (AN) polymer, a PEGMA-TFEA-methyl methacrylate (MMA) polymer, a PEGMA-TFEA-vinylpyrrolidone (VP) polymer, a PEGMA-TFEA-trimethoxyvinylsilane (TMVS) polymer, and a PEGMA-TFEA-ethoxy ethylacrylate (EEA) polymer.

Description

Fluorinated copolymer, contain its polymer dielectric and with this electrolytical lithium cell
The background of invention
Invention field
The present invention relates to the lithium cell of a kind of fluorinated copolymer, polymer dielectric and this polymer dielectric of use, more particularly, the present invention relates to a kind of fluoropolymer, can be as electrochemical apparatus lithium cell and have the good mechanical property and the polymer dielectric of ionic conductivity for example, and by utilizing this polymer dielectric to improve the lithium cell of charge/discharge capabilities.
Description of related art
Fast development along with the relevant industry with computer of various electronicss more and more needs a kind of high efficiency secondary battery.The needed performance of secondary battery that satisfies above-mentioned requirements comprises security, portability, compactness etc.
Usually, the battery that satisfies above-mentioned requirements is the lithium polymer battery of wishing most as secondary battery of future generation, lithium polymer battery can overcome some shortcomings of the lithium ion battery of present popular use, is: safety issue, high Master Cost, be difficult to make or be difficult to obtain high-capacity battery.Have the macroion electric conductivity, for the exploitation of the polymer dielectric of needed good mechanical property of easier processing and high electrochemical stability be the prerequisite that lithium polymer battery is achieved.
Present known polymer battery comprises mixed polymer ionogen, gel-type polymer electrolyte and the analogue that contains organic electrolyte solution.
The problem that the mixed polymer ionogen runs in can the minimum liquid ionogen.Yet still there are some shortcomings in they, comprise the preparation method complicated owing to extract softening agent or dipping electrolyte solution, in view of the safety issue of battery quality, for example leak or are difficult to guarantee repeatability etc.
On the other hand, gel-type polymer electrolyte is like this preparation, and in initial preparation in the stage, solid polymer and organic electrolyte solution that will casting mix.Like this, just do not need to carry out the injection technique of electrolyte solution subsequently.Also have, because electrolyte solution is in initial preparation stage and solvent, so electrolyte solution can be evenly distributed in the entire cell.In addition, because a large amount of liquid electrolytes immerse in the polymeric matrix behind the casting, so ionic conductivity can advantageously improve.
The example of gel-type polymer electrolyte comprises the polymer dielectric of following method preparation, is about to organic electrolyte solution and joins for example preparation in polymethylmethacrylate (PMMA), polyacrylonitrile (PAN) or the polyvinyl chloride (PVC) of fluoropolymer resin.This polymer dielectric is to be made by the fluoropolymer resin with dipole moment, and wherein lithium salts is dissolved in the organic solvent, when organic solvent and lithium salts with the best when mixing, have 10 under the room temperature -3S/cm or higher ionic conductivity.Yet, gel-type polymer electrolyte still has some problems, Fu Za battery preparation method for example, or having increased expense, the increase of this expense is because the preparation method of gel-type polymer electrolyte has high viscosity when needing drying step under 100 ℃ or the higher temperature and resin fusion.
Another example of gel-type polymer electrolyte is disclosed among the Japanese patent application JP03-207752A, and wherein polymer dielectric shines and prepares by ethylene glycol and dimethacrylate being mixed and carrying out UV.The ionic conductivity of this gel-type polymer electrolyte is 10 -4S/cm or littler, and too soft, and thermofixation during the UV irradiation can not further be shaped.Also have, in the battery manufacturing processed, it is bigger relatively that the slit between each electrode and the polymer dielectric becomes, and increased the interface resistance between electrode and the polymer dielectric thus, makes gel-type polymer electrolyte be difficult in practice as secondary battery.
US4,830,939A discloses a kind of polymer dielectric, is the polymerisable monomer by will having one or more unsaturated functional groups and electrolyte solution mixes and solidify by the UV irradiation and to prepare.Although this polymer dielectric has good ionic conductivity, disadvantageously it has poor snappiness.
US5,463,179 disclose a kind of method that improves the polymer dielectric ionic conductivity, are the functional groups by introducing relative rigidity in the polymeric matrix that forms polymer dielectric, and the three-dimensional stable space of formation is realized between the molecule of polymkeric substance.
Yet, according to this method, even the ionic conductivity of polymer dielectric is increased to about 4 * 10 -3S/cm, but the interface resistance between electrode and the polymer dielectric still correspondingly increases, and causes the battery performance variation, makes that polymer dielectric is difficult to use in practice.
The concise and to the point description of invention
In order to address the above problem, the present invention first provides fluoropolymer, its preparation method and the polymer dielectric by using this fluoropolymer to prepare to the 3rd purpose, and described fluoropolymer can increase the lithium ion electric conductivity by the dipping of optimizing organic electrolyte solution and can prepare the polymer dielectric with good mechanical property.
The 4th purpose of the present invention is to have the lithium cell that has improved charge/discharge capabilities by using polymer dielectric to provide.
In order to reach first purpose of the present invention, the invention provides a kind of fluorinated copolymer of representing with general formula 1: formula 1
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
When z in the general formula 1 was not 0, z was 100-1,500.
Fluorinated copolymer is selected from polyethylene glycol monomethyl ether (methyl) acrylate (PEG (M) A)-2,2,2-trifluoroethyl acrylate (TFEA) multipolymer, PEGMA-TFEA-vinyl cyanide (AN) multipolymer, PEGMA-TFEA-methyl methacrylate (MMA) multipolymer, PEGMA-TFEA-vinyl pyrrolidone (VP) multipolymer, PEGMA-TFEA-trimethoxy vinyl silanes (TMVS) multipolymer and PEGMA-TFEA-ethoxyethyl group acrylate (EEA) multipolymer.
The weight-average molecular weight of fluorinated copolymer is 15,000-1,000,000.
In order to reach second purpose of the present invention, the invention provides a kind of method for preparing the fluorinated copolymer of general formula 1 expression, comprise 2 of PEG (M) A of general formula 2 expression and general formula 3 expressions, 2, the monomer mixture of 2-trifluoroethyl (methyl) acrylate (TFE (M) A) carries out solution polymerization: formula 2
Figure A0212704100101
Formula 3
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100103
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
The content of PEG (M) A is the 10-50% mole, and the content of TFE (M) A is the 50-90% mole.
Among the present invention, also add the monomer of general formula 4 expressions in monomer mixture, at this moment, monomer mixture is by PEG (M) A of 5-50% mole, the monomer of general formula 4 expressions of the TFE of 5-50% mole (M) A and 5-90% mole: formula 4
Wherein, R 3Be H or CH independently 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100105
The weight-average molecular weight of PEGMA is 150-2,100.
In order to reach the 3rd purpose of the present invention, the invention provides a kind of polymer dielectric that contains the fluorinated copolymer of general formula 1 expression: formula 1
Figure A0212704100111
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100112
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
This polymer dielectric contains and comprises and be selected from LiClO 4, LiCF 3SO 3, LiPF 6, LiN (CF 3SO 2) 2And LiBF 4Lithium salts, its content is counted the 5-50 weight part with 100 weight part fluorinated copolymers.Also have, in order to improve mechanical property and ionic conductivity, this polymer dielectric also contains the polyoxyethylene glycol dimethyl ether, and the content of this polyoxyethylene glycol dimethyl ether is counted the 10-200 weight part with 100 weight part fluorinated copolymers.
In addition, this polymer dielectric further comprises the organic solvent that is selected from following solvents: ethylene carbonate (EC), propylene glycol carbonic ether (PC), methylcarbonate (DMC), ethyl-carbonate methyl esters (EMC), dipropyl carbonate, diethoxyethane, glycol dimethyl ether, gamma-butyrolactone, dioxolane, tetramethylene sulfone, diethylene glycol dimethyl ether and TEG dimethyl ether, the content of this organic solvent is counted the 50-400 weight part with 100 weight part fluorinated copolymers.
Polymer dielectric of the present invention also further contains the ceramic packing that is selected from silica, aluminum oxide, lithium aluminate and zeolite, and the content of this ceramic packing is counted the 10-50 weight part with 100 weight part fluorinated copolymers.
In order to reach the 4th purpose of the present invention, the invention provides a kind of lithium cell that comprises negative electrode, anode and place negative electrode anode intermediary polymer dielectric, polymer dielectric wherein contains the fluorinated copolymer of general formula 1 expression: formula 1
Figure A0212704100121
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100122
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
In lithium cell of the present invention, negative electrode contains sulphur, and anode is the lithium metallic membrane.In addition, lithium cell of the present invention comprises containing and is selected from LiCoO 2, LiNiO 2, LiMnO 2And LiMn 2O 4Lithium composite xoide negative electrode and contain the anode of carbon or graphite.
Brief description of drawings
Above-mentioned purpose of the present invention and advantage will become clearer by the preferred implementation of describing in detail with reference to following accompanying drawing.
Fig. 1 represents the polyethylene glycol monomethyl ether methacrylic ester-2,2 of synthetic embodiment 1 preparation of the present invention, 2-trifluoroethyl acrylate copolymer 1The H-NMR spectrogram.
Fig. 2 represents the polyethylene glycol monomethyl ether methacrylic ester-2,2 of synthetic embodiment 2 preparations of the present invention, 2-trifluoroethyl acrylic ester-acrylonitrile multipolymer 1The H-NMR spectrogram.
Fig. 3 represents that the ionic conductivity of the polymer dielectrics of the embodiment of the invention 8 and 9 preparations changes with the variation of polyoxyethylene glycol dimethyl ether content.
Fig. 4 represents that the ionic conductivity of the polymer dielectric of the embodiment of the invention 9 preparation changes with the variation of lithium salt content.
Fig. 5 utilizes the diagrammatic sketch of differential scanning calorimeter (DSC) to the heat analysis data of the polymer dielectrics of the multipolymer of synthetic embodiment 2 preparations and the embodiment of the invention 8 and 9 preparations.
Fig. 6 represents the formation curve of the lithium polymer battery of preparation in the embodiment of the invention 12.
Fig. 7 represents the formation curve of the lithium salts/sulphur battery of the embodiment of the invention 13 preparations.
Detailed description of the present invention
The invention provides the fluorinated copolymer { PEG (M) A-TFE (M) A-X copolymer } of general formula 1 expression:
Formula 1
Figure A0212704100131
Wherein, R1、R 2And R3Be H or CH independently respectively3，R 4Be selected from-C ≡ N-C (=O) OCH3The group that represents with following structural formula:
Figure A0212704100132
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
When z was 0, the compound of general formula 1 expression was bipolymer, and when z was not 0, the compound of general formula 1 expression was terpolymer. Under the latter event, z is 100-1,500 more preferably.
Understanding according to mutual-through type, the fluorinated copolymer of general formula 1 expression comprises PEG (M) A and TFE (M) A as the repetitive of necessity, and acrylonitrile (AN), methyl methacrylate (MMA), vinyl pyrrolidone (VP), trimethoxy vinyl silanes (TMVS) and acrylic acid ethoxy ethyl ester (EEA) conduct be repetitive optionally.
The glass transition temperature of fluorinated copolymer is preferably-50 ℃ to-30 ℃, and its weight average molecular weight is 15,000-1, and 000,000, more preferably 15,000-200,000. If the weight average molecular weight of fluorinated copolymer surpasses above-mentioned scope, to the elective reduction of solvent. If the weight average molecular weight of fluorinated copolymer is lower than above-mentioned scope, its mechanical property is with regard to variation.
In order to estimate the hot property of copolymer of the present invention and polymer dielectric, utilize DSC to carry out heat analysis, the result is illustrated among Fig. 5.
Because fluorinated copolymer according to the present invention contains acrylate group, so it can react with lithium ion. Poly-ethylidene oxygen among PEG (M) A has promoted the movement of free lithium ion, has improved thus ionic conductance. TFE (M) A end contain the mechanical property that fluoroalkyl has improved the polymeric layer that is comprised of fluorinated copolymer, make thus the preparation film become possibility. Selective repetitive (X) has increased the affinity to electrolyte solution, allows to introduce required functional group. For example, in order to reach electrochemical stability and to increase dielectric constant, can introduce especially the acrylonitrile (AN) in the above-mentioned repetitive.
The method that the present invention prepares the fluorinated copolymer of general formula 1 expression will be described now.
The fluorinated copolymer of general formula 1 expression is that perhaps the fluorinated copolymer of general formula 1 expression is like this preparation by the copolymerization preparation of TFE (M) A of PEG (M) A of general formula 2 expressions and general formula 3 expressions: the monomer of general formula 4 expressions is joined in the monomer mixture of TFE (M) A of PEG (M) A of general formula 2 expressions and general formula 3 expressions and make their copolymerization: formula 2 formulas 3 formulas 4
Figure A0212704100141
Figure A0212704100142
   
Wherein, R1、R 2And R3Be H or CH independently respectively3，R 4Be selected from-C ≡ N-C (=O) OCH3The group that represents with following structural formula:
Figure A0212704100144
And n is 1-45.
The condition of copolyreaction is not particularly limited, and what the present invention used is polymerisation in solution.
In the polymerisation in solution, add solvent to carry out addition polymerization. According to this technology, keep the flowability of reactant mixture until polymerization is finished, the easy like this reaction heat of removing obtains homogeneous polymer thus. Preferred copolymerization temperature is 70-90 ℃, and the preferred reaction time is 4-24 hour. In addition, the reaction dissolvent of polymerisation in solution depends on that the kind of used monomer, the example comprise oxolane, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxs.
In order to improve reactivity, can use benzoyl peroxide (benzoil peroxide) or azodiisobutyronitrile to be the polymerization initiator of representative. In 100 weight portion monomers, from the angle of reaction yield, the content of polymerization initiator is preferably the 0.1-1 weight portion.
In the polymerization process, the content of polyethylene glycol monomethyl ether (methyl) acrylate is preferably the 10-50% mole, and the content of 2,2,2-trifluoroethyl (methyl) acrylate is preferably the 50-90% mole. When further adding the monomer of general formula 4 expressions in the monomer mixture, the content of polyethylene glycol monomethyl ether (methyl) acrylate is preferably the 5-50% mole, 2,2, the content of 2-trifluoroethyl (methyl) acrylate is preferably the 5-50% mole, and the content of monomer of general formula 4 expressions is preferably the 5-90% mole. If the content of PEG (M) A is lower than above-mentioned scope, the ionic conductance variation of copolymer. If the content of PEG (M) A surpasses above-mentioned scope, the degree of crystallinity of copolymer increases. In addition, if the content of TFE (M) A is lower than above-mentioned scope, the mechanical property variation of copolymer. If the content of TFE (M) A surpasses above-mentioned scope, the ionic conductance of copolymer adversely reduces. If the content of monomer of general formula 4 expressions is lower than above-mentioned scope, the mechanical property variation of copolymer, and the affinity of electrolyte solution reduces. If the content of monomer of general formula 4 expressions surpasses above-mentioned scope, the ionic conductance of copolymer adversely reduces.
In the polymerization process, the weight average molecular weight of PEG (M) A is preferably 150-2, and 100,300-1 more preferably, 100. If the weight average molecular weight of PEG (M) A is high greater than the degree of crystallinity of 2,100, PEG (M) A, causing thus, the degree of crystallinity of the copolymer of preparation increases.
The fluorinated copolymer of general formula 1 expression by using thus preparation, can prepare have high mechanical strength, high ionic conductance and improved polymer dielectric to electrode adhesion power. These polymer dielectrics can have no restrictedly to use, and are advantageously used in lithium battery. Particularly, these polymer dielectrics can use the lithium composite oxide of metal to do to make gel or solid polymer electrolyte in the lithium polymer battery of active material of cathode, more advantageously are to do to make polymer dielectric in the lithium metal of anode/sulphur battery using sulphur to make active material of cathode, lithium metal.
Polymer dielectric according to the present invention contains fluorinated copolymer and the lithium salts of general formula 1 expression, perhaps contains the fluorinated copolymer of general formula 1 expression and the electrolyte solution that is comprised of lithium salts and organic solution. Polymer dielectric prepares by following method.
At first, the fluorinated copolymer that general formula 1 is represented and lithium salts are dissolved in the first organic solvent and prepare polymer electrolyte composition. At this moment, the preferred embodiment of fluorinated copolymer comprises PEGMA-TFEA copolymer, PEGMA-TFEA-AN copolymer, PEGMA-TFEA-MMA copolymer, PEGMA-TFEA-VP copolymer, PEGMA-TFEA-TMVS copolymer, PEGMA-TFEA-EEA copolymer and their mixture. Particularly, x is preferably 5-200, and y is preferably 10-800, and z is preferably 100-1, and 500, n is 4-23. In these scopes, polymer dielectric has the lithium ion electrical conductance that good mechanical property is become reconciled.
The example of lithium salts comprises LiClO4，LiCF 3SO 3，LiPF 6，LiN(CF 3SO 2) 2And LiBF4, in 100 weight portion fluorinated copolymers, its content is preferably the 5-50 weight portion. If the content of lithium salts is lower than 5 weight portions, the ionic conductance of copolymer is low. If the content of lithium salts is higher than 50 weight portions, the restructuring of lithium ion and the precipitation of lithium just adversely occur.
Any organic solvent of dissolving fluorinated copolymer and lithium salts can be used as the first organic solvent, and the example comprises acetonitrile (ACN), oxolane and acetone. In 100 weight portion fluorinated copolymers, the content of the first organic solvent is preferably the 200-800 weight portion. When the content of the first organic solvent in above-mentioned scope, can easily carry out the coating of polymer electrolyte composition.
Then, independently carrier film or composition for electrodes apply and are dry, obtain thus polymer dielectric. Drying is to carry out under room temperature or 50 ℃, to remove the component of the first organic solvent. As the carrier film, can use glass basis, polyester film, pet film or polytetrafluoroethylene film.
The coating of polymer electrolyte composition is not limited to specific method, preferably uses doctor blade method.
Can also further in composition, add polyoxyethylene glycol dimethyl ether (PEGDME) and form polymer dielectric of the present invention as the oligopolymer additive.The interpolation of PEGDME has improved the mechanical property and the ionic conductivity of polymer dielectric.In 100 weight part fluorinated copolymers, its content is preferably the 10-200 weight part, more preferably the 50-150 weight part.If PEGDME content surpasses 200 weight parts, the mechanical strength of polymer dielectric reduces unfriendly.If PEGDME content is lower than 10 weight parts, the effect that improves the polymer dielectric ionic conductivity is just very little.
In addition, can further in polymer electrolyte composition, add second organic solvent that forms electrolyte solution.The available example of this second organic solvent comprises that one or more are selected from ethylene carbonate (EC), propylene glycol carbonic ether (PC), methylcarbonate (DMC), ethyl-carbonate methyl esters (EMC), dipropyl carbonate, diethoxyethane, glycol dimethyl ether, gamma-butyrolactone, dioxolane, tetramethylene sulfone, diethylene glycol dimethyl ether and TEG dimethyl ether.In 100 weight part fluorinated copolymers, the content of this second organic solvent is the 50-400 weight part.
Sometimes, in order to improve mechanical strength and ionic conductivity, in the preparation polymer electrolyte composition, can further add ceramic packing.
The example of available ceramic packing comprises silica, aluminum oxide, lithium aluminate and zeolite.In 100 weight part fluorinated copolymers, the content of this ceramic packing is preferably the 10-50 weight part.If, adding the effect that ceramic packing produced less than 10 weight parts, the content of ceramic packing almost can't see.If the content of ceramic packing is greater than 50 weight parts, the viscosity of polymer electrolyte composition sharply increases.
Zhi Bei polymer dielectric of the present invention is solid type or the gel-type that does not contain or contain a small amount of second organic solvent thus.Owing to contain fluorine in the polymer dielectric, so it has fabulous mechanical property and high ionic conductivity.
Below, will method that use polymer dielectric of the present invention to prepare lithium two-pole cell be described.
At first, utilize ordinary method to prepare negative electrode and anode.Active material as negative electrode is not particularly limited, and its useful examples comprises for example LiCoO of lithium composite xoide 2, LiNiO 2, LiMnO 2Or LiMn 2O 4And sulphur.For active material of positive electrode, can use carbon or graphite.In addition, the film of itself being made by the lithium metal also can be used as anode.Sometimes, negative electrode and anode can digest in electrolyte solution, and electrolyte solution is soaked full negative electrode and anode.At this moment, electrolyte solution is made up of the lithium salts and second organic solvent that are used to prepare polymer dielectric.If electrolyte solution soaks full negative electrode and anode in this manner, the movability of lithium ion improves, and has improved ionic conductivity thus.Then, negative electrode and anode are separately fixed on the carrier film.
Subsequently, the polymer electrolyte composition casting of method for preparing is on the negative electrode and/or anode that are supported on the carrier film, and dry, prepared polymer dielectric thus.Polymer dielectric with preparation inserts between negative electrode and the anode then.
As mentioned above, polymer dielectric by with the composition casting on negative electrode and/or anode and dry products obtained therefrom make.In addition, can become independent carrier film and drying, then polymer dielectric be peeled off from carrier film with the polymer electrolyte composition casting.Subsequently, will insert between negative electrode and the anode, form the electrode assemblie of battery thus from the polymer dielectric that carrier film is peeled off.
Among the present invention, can also between negative electrode (or anode) and polymer dielectric, insert sealing coat.At this moment, any have cancellated insulating material and can be used as sealing coat.Be provided at the mechanical property that sealing coat in the polymer dielectric has improved polymer dielectric.
The example of sealing coat comprises monolayer polyethylene film, double-layer polyethylene/polypropylene or three-layer polyethylene/polypropylene, polyethylene.The thickness of sealing coat is preferably 9-40 μ m, and its hole is preferably 30-70%.
Lithium cell of the present invention is not particularly limited its type, not only comprises lithium primary cell but also comprise lithium two-pole cell.Particularly, preferably have negative electrode that sulphur forms and lithium metallic film as anodic lithium metal/sulphur secondary battery according to lithium cell of the present invention, or have for example LiCoO of lithium-metal composite oxides 2The anodic lighium polymer secondary battery that negative electrode of forming and carbon or graphite are formed.
Below, the present invention will be explained in more detail with reference to the following examples, and described embodiment never limits the present invention.
Synthetic embodiment 1
N 2Protection down; in reaction flask, add 15.41g (0.1mol) 2; 2; 2-trifluoroethyl acrylate (TFEA), 27.5g (0.025mol) weight-average molecular weight are 1100 polyethylene glycol monomethyl ether methacrylic ester (PEGMA); make it to be dissolved in the 150ml tetrahydrofuran (THF); add the 0.05g benzoyl peroxide subsequently, carry out solution polymerization under 80 ℃.Along with reaction is carried out, made full-bodied yellow solution.Solution polymerization was carried out about 18 hours.Then, in reaction mixture, add pentane, obtain yellow solid as non-solvent.Solid about 24 hours of 80 ℃ of following vacuum-dryings, has been synthesized PEGMA-TFEA multipolymer (hereinafter being called " FAMP ") thus, and productive rate is 95%.
The PEGMA-TFEA multipolymer is used 1H-NMR analyzes, and analytical results is illustrated among Fig. 1, confirms thus, and the mol ratio that PEGMA and TFEA exist is 1: 4.The weight-average molecular weight of multipolymer is approximately 16,000, x=9, y=36 and n=23.
Synthetic embodiment 2
Except further in PEGMA and TFEA mixture, adding 60g (1.13mol) acetonitrile, synthesized PEGMA-TFEA-AN multipolymer (being called " TAMP " hereinafter) according to the method identical with synthetic embodiment 1, productive rate is 45%.
The PEGMA-TFEA-AN multipolymer is used 1H-NMR analyzes, and analytical results is illustrated among Fig. 2.The weight-average molecular weight of multipolymer is approximately 45,000, x=24, y=28, z=288 and n=23.
Synthetic embodiment 3-6
Except replacing AN to add MMA, VP, TMVS and the EEA respectively, according to method respectively synthetic PEGMA-TFEA-MMA multipolymer, PEGMA-TFEA-VP multipolymer, PEGMA-TFEA-TMVS multipolymer and the PEGMA-TFEA-EEA multipolymer identical with synthetic embodiment 2.The weight-average molecular weight of PEGMA-TFEA-MMA multipolymer is approximately 87,000, x=22, y=55, z=506 and n=23.The weight-average molecular weight of PEGMA-TFEA-VP multipolymer is approximately 130,000, x=21, y=74, z=840 and n=23.The weight-average molecular weight of PEGMA-TFEA-TMVS multipolymer is approximately 43,000, x=14, y=28, z=168 and n=23.The weight-average molecular weight of PEGMA-TFEA-EEA multipolymer is approximately 120,000, x=18, y=56, z=612 and n=23.
Embodiment 1
With 0.2g LiCF 3SO 3Join 2g PEGMA and TFEA mol ratio and be in 1: 1 the PEGMA-TFEA multipolymer, and be dissolved in fully among the 5gACN, utilize scraper to be coated on the glass matrix then.Subsequently, dry the removing of resulting product desolvated, made polymer dielectric thus.
Embodiment 2-5
Except the mol ratio of PEGMA and TFEA in the PEGMA-TFEA multipolymer becomes 1: 3 respectively, 1: 5, outside 1: 7 and 1: 10, prepare polymer dielectric according to the method identical with embodiment 1.
The polymer dielectric for preparing among the embodiment 1-5 is tested its ionic conductivity and mechanical property, and its result is illustrated in the table 1.At this, ionic conductivity is that to form film and be cut into area at polymer dielectric be 1cm 2Test during size.Mechanical property is to estimate by the easy processing stage of film.
Table 1
The mol ratio of PEGMA and TFEA in the PEGMA-TFEA multipolymer
????1∶1 ????1∶3 ????1∶5 ????1∶7 ????1∶10
Ionic conductivity (S/cm) ????5.26×10 -5 ????3.82×10 -5 ????2.58×10 -5 ????6.84×10 -6 ????1.83×10 -6
Mechanical property Difference Difference Good Good Excellent
As can be confirmed from Table 1, along with the increase of PEGMA content, the mechanical property variation of polymer dielectric, along with the increase of TFEA content, its ionic conductivity becomes poorer.
Embodiment 6
In 0.025mol PEGMA and 0.125mol TFEA mixture, add the monomer that 0.5mol is selected from AN, MMA, VP, TMVS and EEA respectively, and reaction, prepared the PEGMA-TFEA-X terpolymer thus, wherein X is AN, MMA, VP, TMVS and EEA.
(EC/PC blended volume ratio is the 1.0M LiPF in 1: 1 to add electrolyte solution in each terpolymer 6).In 100 weight part terpolymers, the content of every kind of terpolymer is 200 weight parts.
Tested the ionic conductivity of gel-type polymer electrolyte, the results are shown in the table 2.
Table 2
The PEGMA-TFEA-X terpolymer
The X monomer ????AN ????MMA ????VP ????TMVS ????EEA
Ionic conductivity (S/cm) 2.35×10 -3 6.67×10 -4 ?1.83×10 -3 3.97×10 -4 5.18×10 -4
Mechanical property Good Excellent Good Good Excellent
As can be seen from Table 2, ionic conductivity changes ground and little with the kind of used monomer X, and when monomer X was acrylate-based monomer, mechanical property was good especially.
Embodiment 7
In 100 weight part multipolymers, add lithium salts (LiCF in the 2gTAMP multipolymer that in embodiment 6, prepares according to the amount of listing in the table 3 3SO 3), and be dissolved among the 5gACN, be coated on the glass matrix with scraper subsequently.Subsequently, the resulting product drying at room temperature except that desolvating, has been made solid polymer electrolyte thus.
Mechanical strength and ionic conductivity according to the solid polymer electrolyte of the method test preparation identical with embodiment 2.Mechanical strength will be high enough to carry out film and handle, and ionic conductivity is illustrated in the table 3.
Table 3
????1 ????2 ????3 ????4
??LiCF 3SO 3Content 5 weight parts 10 weight parts 15 weight parts 20 weight parts
Ionic conductivity (S/cm) ??5.23×10 -8 ????8.52×10 -8 ????1.37×10 -7 ????4.68×10 -7
Reference table 3 as can be seen, the solid polymer electrolyte of embodiment 7 preparation has better ionic conductivity along with the increase of lithium salt content.
Embodiment 8
In embodiment 6, add weight-average molecular weight in the preparation TAMP multipolymer and be 250 polyoxyethylene glycol dimethyl ether (being abbreviated as " PEGDME 250 ") and LiCF 3SO 3, and be dissolved among the ACN, be coated on the glass matrix with scraper subsequently.At this, unless otherwise mentioned, all content of each component are represented with " weight part ".
Subsequently, dry removing under the resulting product room temperature desolvated, prepared polymer dielectric thus.
The ionic conductivity of the polymer dielectric of test preparation the results are shown in the table 4.
Table 4
????1 ????2 ????3 ????4 ????5 ????6 ????7
?TMAP ????0.4 ????0.5 ????0.6 ????0.7 ????0.8 ????0.85 ????0.9
?PEGDME?250 ????0.6 ????0.5 ????0.4 ????0.3 ????0.2 ????0.15 ????0.1
?LiCF 3SO 3 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
?CAN ????3 ????3 ????4 ????4 ????5 ????5 ????5
Ionic conductivity (S/cm) 9.67×10 -5 ?6.51×10 -5 ?2.75×10 -5 8.50×10 -6 ?1.55×10 -6 ?8.41×10 -7 6.15×10 -7
As can be confirmed from Table 4, the ionic conductivity of polymer dielectric increases with the increase of PEGDME content.
Embodiment 9
Except being that 500 polyoxyethylene glycol dimethyl ether (being abbreviated as " PEGDME500 ") replaces the PEGDME 250 with weight-average molecular weight, prepare polymer dielectric according to the method identical with embodiment 8.
The ionic conductivity of the polymer dielectric of test preparation, the result is illustrated in the table 5.In the table 5, unless otherwise mentioned, all content of each component are represented with " weight part ".
Table 5
????1 ????2 ????3 ????4 ????5 ????6 ????7
?TMAP ????0.4 ????0.5 ????0.6 ????0.7 ????0.8 ????0.85 ????0.9
?PEGDME?500 ????0.6 ????0.5 ????0.4 ????0.3 ????0.2 ????0.15 ????0.1
?LiCF 3SO 3 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
?CAN ????3 ????3 ????4 ????4 ????5 ????5 ????5
Ionic conductivity (S/cm) 3.60×10 -5 1.98×10 -5 ?7.56×10 -6 ?6.54×10 -6 1.45×10 -6 ?7.69×10 -7 6.36×10 -7
The ionic conductivity that is appreciated that polymer dielectric from table 5 increases along with the increase of PEGDME content.
Fig. 3 has represented that the ionic conductivity of the polymer dielectric of preparation among the embodiment 8 and 9 changes along with the variation of PEGDME content.
With reference to figure 3, suppose that the composition of the polymer dielectric of preparation is identical, use the ionic conductivity height of PEGDME250 than the polymer dielectric that uses PEGDME 500.
Embodiment 10
50 weight part TAMP of embodiment 6 preparation are joined 50 weight part PEGDME 250 and consumption is respectively 5,10,15 and 20 weight part LiCF 3SO 3In, and be dissolved among the 300 weight part ACN, be coated on the glass matrix with scraper subsequently.Subsequently, dry removing under the resulting product room temperature desolvated, prepared polymer dielectric thus.
Also have, the TAMP of 50 weight part embodiment, 6 preparations is joined 50 weight part PEGDME500 and consumption is respectively 5,10,15 and 20 weight part LiCF 3SO 3In, and be dissolved among the 300 weight part ACN, be coated on the glass matrix with scraper subsequently.Subsequently, dry removing under the resulting product room temperature desolvated, prepared polymer dielectric thus.
The mechanical strength and the ionic conductivity of the solid polymer electrolyte of test preparation.The result shows that mechanical strength is high enough to is convenient to film processing, and ionic conductivity is illustrated among Fig. 4.
With reference to figure 4, work as LiCF 3SO 3When content is approximately 10 weight parts, utilize the polymer dielectric of PEGDME 250 preparations to have the highest ionic conductivity.Also have, work as LiCF 3SO 3When content is approximately 15 weight parts, utilize the polymer dielectric of PEGDME 500 preparations to have the highest ionic conductivity.
Embodiment 11
The FAMP and the TAMP multipolymer of preparation among the synthetic embodiment 1 and 2 are mixed, wherein add PEGDME 250 and LiCF 3SO 3, be coated on the glass matrix with scraper subsequently.Each components contents is changed according to the amount of listing in the table 6, and unless otherwise mentioned, all content of each component are represented with " weight part ".
Table 6
????1 ????2 ????3 ????4
?FAMP ????0.1 ????0.2 ????0.1 ????0.2
?TMAP ????0.4 ????0.4 ????0.3 ????0.3
?PEGDME?250 ????0.5 ????0.4 ????0.6 ????0.5
?LiCF 3SO 3 ????0.1 ????0.1 ????0.1 ????0.1
Ionic conductivity (S/cm) ??5.47×10 -5 ??9.05×10 -6 ????1.56×10 -4 ????7.18×10 -5
Reference table 6, when adding a small amount of FAMP, the content of TAMP reduces, and PEGDME content increases, and the movability that this has promoted lithium ion has increased the ionic conductivity of polymer dielectric.
Embodiment 12
With 68.5 weight part LiCoO 2, super P of 1.5 weight parts and 1.5 weight part fluorinated ethylene propylenes and 28.5 weight part NMP are mixed with the formation cathode compositions.Then, cathode compositions applies and drying with forming with the aluminium current collector, has made negative electrode thus.
53.6 weight part carbon, 3.4 weight part polyvinyl chloride and 43 weight part NMP are mixed and made into formation anodic composition.Then, with forming anodic composition coated copper current collector and dry, made anode thus.
With the preparation negative electrode and anode pickling (EC/PC mixed volume ratio is the 1.0M LiPF in 1: 1 at electrolyte solution 6) in, make electrolyte solution soak full negative electrode and anode.
Utilize double sticky tape that negative electrode and anode are fixed on the polyester film.200 weight part electrolyte solutions are joined in the polymer electrolyte composition, and said composition is dissolved in 100 weight part TAMP among the 300 weight part ACN and prepares, and uses polymer dielectric coated cathode and anode then.
Subsequently, polyester film is removed from resulting product.Then, polyethylene isolation layer is placed in the polymer dielectric, and fixing with glass to make it and can not move.Electrode terminal is adhered on the products obtained therefrom, twines and sealing with blue sack, under high pressure negative electrode is made in compression subsequently, with polymer dielectric and anode close adhesion, finishes lithium polymer battery thus.
Embodiment 13
55 weight part sulphur, the super P of 28 weight parts and 17 weight part polyethylene oxides are mixed with the cathode active material feed composition.Cathode current collector is applied and drying with the cathode active material feed composition, make negative electrode.
Use lithium metallic membrane itself to make anode.
To be placed on the lithium anodes with the polyethylene isolation layer that polymer dielectric applies, and the negative electrode of preparation is placed on the polymer dielectric, made lithium metal/sulphur battery thus.The polyethylene isolation layer that applies with polymer dielectric prepares according to following method.
By with 50 weight part TAMP, 50 weight part PEGMDE 250 and 10 weight part LiCF 3SO 3Be dissolved among the 300 weight part ACN and make polymer electrolyte composition.Be immersed in this polymer electrolyte composition polyethylene film and drying, make the polyethylene isolation layer that applies with polymer dielectric.
The lithium polymer battery that embodiment 12 is made carries out the charge/discharge cycle test, and the result is illustrated in the table 6.Charge/discharge cycle test is to be that 0.2C, voltage are to carry out under the condition of 2.7-4.2V at current rate.
With reference to figure 6, the starting stage in charging and discharge, under the situation at the side reaction peak that does not exist electrode and ionogen to cause, have highly stable charging and discharge condition.
Then, lithium metal/sulphur polymer battery that embodiment 13 is prepared carries out the charge/discharge cycle test, and the result is illustrated among Fig. 7.The test of this charge/discharge cycle is to be that 0.25C, voltage are to carry out under the condition of 1.5-2.8V at current rate.
Compare with only using the conventional liq ionogen, better bounding force is given the credit to and has been used polymer dielectric between polymer dielectric and the electrode.Also have, as shown in Figure 7, the loading capacity that obtains approaches the theoretical capacity of sulphur, and promptly 1674mAh/g this means, polymer dielectric can increase the reversibility of the polysulfide that produces in lithium metal/sulphur battery.
According to the present invention, the fluorinated copolymer of general formula 1 expression has low degree of crystallinity, and the result is not hindering under the ambulant situation of lithium ion, is being good aspect mechanical property, thermostability and the chemical stability.
When fluorinated copolymer of the present invention was used as polymer dielectric, the polymer dielectric of preparation had following advantage.
First because fluorinated copolymer has low degree of crystallinity, and its working (machining) efficiency is high, because therefore its good mechanical property can easily make film.
The second and since have in low-down degree of crystallinity and the polymer substrate under the fluorinated copolymer room temperature exist can mobile lithium ion component, so fluorinated copolymer can not contain or contain under a small amount of electrolyte solution as solid electrolyte. Therefore, there is not generation owing to the side reaction of using excessive electrolyte to cause.
The 3rd, have good bonding force between polymer dielectric and the electrode.
The lithium battery that use has the polymer dielectric preparation of above-mentioned advantage has improved the chemical property that comprises high ionic conductance, the charge/discharge cycle performance of becoming reconciled.

Claims (22)

1, a kind of fluorinated copolymer of general formula 1 expression: formula 1
Figure A0212704100021
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
2, according to the fluorinated copolymer of claim 1, wherein when z in the general formula 1 was not 0, z was 100-1,500.
3, according to the fluorinated copolymer of claim 1, wherein fluorinated copolymer is selected from polyethylene glycol monomethyl ether (methyl) acrylate (PEG (M) A)-2,2,2-trifluoroethyl acrylate (TFEA) multipolymer, PEGMA-TFEA-vinyl cyanide (AN) multipolymer, PEGMA-TFEA-methyl methacrylate (MMA) multipolymer, PEGMA-TFEA-vinyl pyrrolidone (VP) multipolymer, PEGMA-TFEA-trimethoxy vinyl silanes (TMVS) multipolymer and PEGMA-TFEA-ethoxyethyl group acrylate (EEA) multipolymer.
4, according to the fluorinated copolymer of claim 1, wherein the weight-average molecular weight of fluorinated copolymer is 15,000-1,000,000.
5, a kind of method for preparing the fluorinated copolymer of general formula 1 expression comprises that the monomer mixture of 2-trifluoroethyl (methyl) acrylate (TFE (M) A) carries out solution polymerization: formula 2 with 2,2 of PEG (M) A of general formula 2 expressions and general formula 3 expressions Formula 3
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100032
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
6 methods according to claim 5, wherein the content of PEG (M) A is the 10-50% mole, the content of TFE (M) A is the 50-90% mole.
7 methods according to claim 5 wherein also add the monomer that general formula 4 is represented, at this moment, monomer mixture is by PEG (M) A of 5-50% mole, and the monomer of general formula 4 expressions of the TFE of 5-50% mole (M) A and 5-90% mole is formed: formula 4
Wherein, R 3Be H or CH independently 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100034
8, according to the method for claim 5, wherein the weight-average molecular weight of PEGMA is 150-2,100.
9, a kind of polymer dielectric that contains the fluorinated copolymer of general formula 1 expression: formula 1
Figure A0212704100041
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
Figure A0212704100042
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
10, according to the polymer dielectric of claim 9, wherein fluorinated copolymer is selected from polyethylene glycol monomethyl ether (methyl) acrylate (PEG (M) A)-2,2,2-trifluoroethyl acrylate (TFEA) multipolymer, PEGMA-TFEA-vinyl cyanide (AN) multipolymer, PEGMA-TFEA-methyl methacrylate (MMA) multipolymer, PEGMA-TFEA-vinyl pyrrolidone (VP) multipolymer, PEGMA-TFEA-trimethoxy vinyl silanes (TMVS) multipolymer and PEGMA-TFEA-ethoxyethyl group acrylate (EEA) multipolymer.
11,, also contain and be selected from LiClO according to the polymer dielectric of claim 9 4, LiCF 3SO 3, LiPF 6, LiN (CF 3SO 2) 2And LiBF 4Lithium salts, its content is counted the 5-50 weight part with 100 weight part fluorinated copolymers.
12, according to the polymer dielectric of claim 11, also comprise the polyoxyethylene glycol dimethyl ether, the content of this polyoxyethylene glycol dimethyl ether is counted the 10-200 weight part with 100 weight part fluorinated copolymers.
13, according to the polymer dielectric of claim 11, also contain the organic solvent that is selected from following solvents: ethylene carbonate (EC), propylene glycol carbonic ether (PC), methylcarbonate (DMC), ethyl-carbonate methyl esters (EMC), dipropyl carbonate, diethoxyethane, glycol dimethyl ether, gamma-butyrolactone, dioxolane, tetramethylene sulfone, diethylene glycol dimethyl ether and TEG dimethyl ether, the content of this organic solvent is counted the 50-400 weight part with 100 weight part fluorinated copolymers.
14, according to the polymer dielectric of claim 11, also contain the ceramic packing that is selected from silica, aluminum oxide, lithium aluminate and zeolite, the content of this ceramic packing is counted the 10-50 weight part with 100 weight part fluorinated copolymers.
15, a kind of lithium cell that comprises anode, negative electrode and place the polymer dielectric between the negative electrode anode, polymer dielectric wherein contain the fluorinated copolymer of general formula 1 expression: formula 1
Figure A0212704100051
Wherein, R 1, R 2And R 3Be H or CH independently respectively 3, R 4Be selected from-C ≡ N-C (=O) OCH 3The group of representing with following structural formula:
N is 1-45, and x is 5-200, and y is 10-800, and z is 0-2,000.
16, according to the lithium cell of claim 15, wherein negative electrode comprises sulphur, and anode is the lithium metallic membrane.
17, according to the lithium cell of claim 15, wherein negative electrode contains and is selected from LiCoO 2, LiNiO 2, LiMnO 2And LiMn 2O 4Lithium composite xoide, anode contains carbon or graphite.
18, according to the lithium cell of claim 15, wherein fluorinated copolymer is selected from polyethylene glycol monomethyl ether (methyl) acrylate (PEG (M) A)-2,2,2-trifluoroethyl acrylate (TFEA) multipolymer, PEGMA-TFEA-vinyl cyanide (AN) multipolymer, PEGMA-TFEA-methyl methacrylate (MMA) multipolymer, PEGMA-TFEA-vinyl pyrrolidone (VP) multipolymer, PEGMA-TFEA-trimethoxy vinyl silanes (TMVS) multipolymer and PEGMA-TFEA-ethoxyethyl group acrylate (EEA) multipolymer.
19,, also contain and be selected from LiClO according to the lithium cell of claim 15 4, LiCF 3SO 3, LiPF 6, LiN (CF 3SO 2) 2And LiBF 4Lithium salts, its content is counted the 5-50 weight part with 100 weight part fluorinated copolymers.
20, according to the lithium cell of claim 19, also comprise the polyoxyethylene glycol dimethyl ether, the content of this polyoxyethylene glycol dimethyl ether is counted the 10-200 weight part with 100 weight part fluorinated copolymers.
21, according to the lithium cell of claim 19, also contain the organic solvent that is selected from following solvents: ethylene carbonate (EC), propylene glycol carbonic ether (PC), methylcarbonate (DMC), ethyl-carbonate methyl esters (EMC), dipropyl carbonate, diethoxyethane, glycol dimethyl ether, gamma-butyrolactone, dioxolane, tetramethylene sulfone, diethylene glycol dimethyl ether and TEG dimethyl ether, the content of this organic solvent is counted the 50-400 weight part with 100 weight part fluorinated copolymers.
22, according to the lithium cell of claim 19, also contain the ceramic packing that is selected from silica, aluminum oxide, lithium aluminate and zeolite, the content of this ceramic packing is counted the 10-50 weight part with 100 weight part fluorinated copolymers.
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